Organosilicon hydroxyalkyl-amine polymers



$346,259 Patented July 24, 19 52 ice 3,046,250 ORGANGSILICQN HYDROXYALKYL-AMINE POLYMERS Edwin P. Plueddemann, Midland, Mich, assignor to Dow Corning Corporation, Midland, Mich, a corporation of lVIichigan No Drawing. Filed Oct. 4, 1957, Ser. No. 638,118 6 Claims. (Cl. 260-465) This invention relates to new polymers containing silicon atoms joined by organoamino groups which are connected to each silicon through silicon-carbon linkages.

A new class of organosilicon epoxides wherein each epoxy or epoxidized group is attached to the silicon by a silicon-carbon linkage was disclosed in applicants copending application Serial No. 618,669, filed October 29, 1956, which application is incorporated into this application by reference. Applicant has now invented new polymers by reacting those organosilicon epoxides with ammonia and amine compounds.

This invention relates to organosilicon compositions containing at least two silicon atoms bonded by the linkage -XYX in which each Y is a polyvalent radical attached to at least two X radicals by nitrogen-carbon bonds, said Y radical being free of hydrolyzable halogen atoms and acid groups having a dissociation constant greater than l Each X is a polyvalent organic radical connected to silicon by a silicon-carbon linkage and consisting of hydrogen atoms, carbon atoms and oxygen atoms, the latter being present as hydroxyl radicals, epoxy groups or ether linkages, said X radical containing at least one pair of adjacent carbon atoms, one carbon atom of said pair being attached to a hydroxyl group and the other carbon atom of said pair being attached to a nitrogen of the group Y. Each of the remaining valences of the silicon atoms in said silicon composition can be attached to a hydrogen atom, an oxygen atom, an hydroxyl radical, a monovalent hydrocarbon radical, a monovalent halogenohydrocarbon radical, a monovalent hydrocarbonoxy radical or a monovalent halogenohydrocarbonoxy radical.

The crux of this invention lies in the unique XYX linkage between two silicon atoms. The linkage can be straight chain, e.g. ESiXYXSiE, cyclic, e.g.

XYX Si or branched chain, e.g.

ESiXYXSiE X Si I/I SiE X Y ESiXYXSiE Y Y X X Si Si II! III The preferred method of preparation of the linkage of this invention is the reaction of an organosilicon epoxy or epoxidized group of the type disclosed in the aforesaid copending application With ammonia or an amine having at least 2 nitrogen-bonded hydrogens under conditions such as those shown in the subsequent working examples. The simple 1:1 amine-epoxy adducts are described in applicants copending application entitled Organosilicon Epoxide Derivatives. In that case the amine adduct does not contribute to a polymeric structure. The term epoxidized group is employed here to mean an epoxycontaining group.

The organosilicon epoxides employed in applicants preferred method are further described in applicants copending application Serial No. 618,669, filed October 29, 1956. Two basic methods of preparation of these epoxides are shown therein. The first method is the reaction of an organosilicon compound containing a radical having a (:C linkage with peracids such as peracetic, perbenzoic and perpropionic acids, thereby oxidizing the double bond to yield an epoxy group. The second method is that of adding an unsaturated organic compound containing at least one epoxy group to a silicon compound containing at least 1 SiH group preferably in the presence of platinum, ultraviolet light, organic peroxides or other silane addition catalyst. The epoxidized radical can, therefore, consist of an epoxy group connected directly to a silicon atom or can be connected to the silicon through a variety of linking chains. The epoxidized radicals employed herein can also contain more than one epoxy group, for instance, where a butadienyl radical attached to silicon is oxidized with a peracid to produce the corresponding diepoxy radical. The number of free valences of any X equals One plus the number of epoxy groups which were in the group from which that X was derived and which react with N.

Thus X radicals derived from epoxidized radicals can include such radicals as:

on on on {11101121 OHzOHOHz-, CHzOHzOHCHz,

CH2CHZCHZOCH2 OH CHO OHQOHCHR OH CH2CHCH2O CH2 OH OH CHz(O CH2CH2)6O CHCHr, CHzO CHzCHzO CHzCHzCHCHzcrn-cn- OHz-C1[ orr -crr 011011 on H 011F011 CH=CH orno OH -crnon 011-, orncn CHCH2CH2CHCHT- err-Tenor: orr=orr on crnoncmoorncncm- Y in this invention, as stated above, is a polyvalent radical attached to at least two X radicals by nitrogencarbon bonds. It is derived by the preferred method of this invention from ammonia or an organic compound containing at least 2 nitrogen-bonded hydrogens. When this amino-organic compound or ammonia is reacted with a silicon-bonded epoxidized group, a nitrogen-bonded hydrogen leaves the nitrogen atom, the .epoxy group breaks open, the nitrogen atom attaches to one carbon and the free hydrogen atom attaches to the free oxygenvalence, thereby forming an hydroxyalkyl-amine linkage. In order for an amino-organic compound to be operative in this invention, it is necessary that there be at least 2 nitrogen-bonded hydrogens to make possible reaction with 2 ditferent epoxy groups. Thus, Y can be such radicals as IIIH where R is a monovalent organic radical and R is a divalent organic radical, neither of which radicals contain hydrolyzable halogen atoms or acid groups having a dissociation constant greater than l These specific exceptions are necessary since the groups included are sufliciently reactive with epoxy groups that their reaction therewith would substantially interfere with the amine-epoxy reaction.

Examples of halogen atoms readily hydrolyzable at room temperature include acid halides, such as acyl chloride, acyl bromide, acyl iodide and sulfonyl chloride, and silicon-bonded halogen atoms, such as silicon-bonded chlorine, silicon-bonded bromine, silicon-bonded iodine and silicon-bonded fluorine. Examples of acid groups which have a dissociation constant greater than and therefore cannot be present are the sulfonic acid group and acid groups derived from such organic acids as trichloroacetic acid and picric acid. It can be seen, therefore, that the radicals R and R can contain a large variety of different functions.

The R and R groups which can be present in the amino-organic compositions employed in this invention can be, for example, non-functional saturated hydrocarbon radicals or they can be any hydrocarbon radicals which contain any unsaturated function, any nitrogen function, any halogen not readily hydrolyzable at room temperature, any metallic function, any oxygen function and any sulfur function except acid groups with a dissociation constant above 10 More specifically, these functions can contain any groups such as the following: nitrogen functional groups, such as nitro, nitroso, amine, azo, azoxy, imido, and nitrile; unsaturated functions, such as alkene and alkyne linkages; halides such as chlorine, bromine, fluorine and iodine, which are not readily hydrolyzable at room temperature; sulfur functional groups, such as sulfone, sulfoxide, mercaptan, thioaldehyde, thioketone, thioesters and thioether; oxygen functional groups such as hydroxyl, ether, carbonyl (both ketone and aldehyde), carboxyl and ester. It should be understood that the R and R" groups can contain two or more of the above functions in any arrangement within the other limitations of this invention. These functions can be incorporated into any aliphatic, alicyclic or aromatic radicals. Furthermore, any organometallic function or metal oxygen function can be present without interfering with the formation of the claimed composition of this invention.

Thus, amino-organic compounds which react with epoxidized organosiloxane compounds to form the compositions of this invention can include any of the following compounds: ethane semicarbazone, acetaldehydeammonia, acetamide, a,oz-dichloroacetamide, thioacetamide, acetamidine, o-aminoacetophenone, acrylamide, adalin, adipamide, allanturic acid, ethyl ester of allo- -phanic acid, allylamine, ammelide, tert-amylamine, aniline, n-benzohydryl, 2,4-dibromo-6-nitroaniline, o-fiuoroaniline, p-nitrosoaniline, ar-pentachloroaniline, p,p-thiodianiline, anisamide, m-anisidine, 9,10-anthradiamine, anthranilaldehyde, methyl ester of anthranilic acid, 3-mitroanthranilic acid, anthranilonitrile, Z-amino-l-hydroxyanthraquinone, arsanilic acid, L-aspartic acid, p-aminoazobenzene, 5,5 diallylbarbituric acid, 5 (2 furfurylidene)-2-thiobarbituric acid, benzalhydrazine, benzamidoxi-me, benzamidine, benzenepentamine, benzenesulfonamide, 3-ethoxybenzidine, benzidine sulfone, benzocaine, p-aminobenzohydrol, benzohydrazide, 3-arnino-5-nitro- 'benzoic acid, o-sulfamylbenzoic acid, 2,2-diaminobenzophenone, biguanide, acetylbiuret, bornylamine, 2-amin0- butanol, cadaverine, 3-aminocarnphor, dithiocarbamic acid, thiolcarbamic acid-ethyl ester, thionocarbamic acidethyl ester, thiocarbanilide, 1,5diphenylcarbohydrazide, m-aminocinnamic acid, 3-amino-o-cresol, crotonamide, cyanamide, cyclohexylamine, L-cysteine, diethylenetriamine, ethoxyamine, formamide, formohydrazide, D- fructosarnine, guanidine, p-bromophenylhydrazine, piperazine, o-nitrophenylhydrazine, lactarnide, nicotinamide, ethyloxamate, oxamide, pararosaniline, 2-phenanthrylamine, Z-nitrophenetidine, p-aminothiophenol, 2-arninopyridine, 4-aminoquinoline, thiosemicarbazide, sulfanilamine, tetradecylamine, 3-thiophenesulfonamide, thiophenine, a,a,a-trifluoro-m-toluidine, 2-bromo-5-nitro-ptoluidine, urea, allylurea, allylthiourea, ethylideneurea, nitrourea, p-phenethylurea, vinylamine, sulfaguanidine, dimethylgallium amide, and aminophenylmercuric acetate.

This list is not complete but is intended to emphasize the broad scope of the Y radical in the linkage unit of this invention.

Any remaining valences on the silicon atoms of the compounds of this invention can be satisfied by a hydrogen atom, oxygen atom, hydroxyl radical, monovalent hydrocarbon radical, a monovalent halogenohydrocarbon radical, a monovalent hydrocarbonoxy radical, a monovalent halogenohydrocarbonoxy radical or another alkanol-amine linkage to another silicon. The term hydrocarbonoxy radical refers to hydrocarbon radicals containing hydroxyl and/ or epoxy groups and radicals of the formula OR where R is a hydrocarbon radical. The term halogenohydrocarbonoxy radical refers to hydroxylated halogenohydrocarbon radicals and radicals of the formula OR where R is a halogenohydrocarbon radical.

Operative monovalent hydrocarbon radicals include alkyl radicals, such as methyl, ethyl, isobutyl and stearyl; alkenyl radicals, such as vinyl, allyl, methallyl and butadienyl; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and undecahydrodiphenyl; cycloalkenyl radicals, such as cyclopentenyl, 2,6-dimethylcyclooctadienyl and cycloheptadecenyl; aryl radicals, such as phenyl, xcnyl and naphthyl; aralkyl radicals, such as benzyl, and alkaryl radicals, such as tolyl.

Operative monovalent halogenohydrocarbon radicals include, for example, chloromethyl, 3,3-dibromobutyl, 1,2-dichlonovinyl, 2,4,6-triiodocyclohexyl, 2,2-difluorocyclopentene-3,4-yl, a,oz,o-triflIlO10tOlyl, 3,3,3-trifluoropropyl, a,a-dichlorobenzyl and 2-bromo-4,6-diiodophenyl.

As shown above, the remaining valences on the silicon Example 1 BICIHIIS can be satisfied by oxygen atoms attached to monova ent h drocarbon and halo enoh drocarbon radicfls, hydrgcarbonoxy and halocgmohglldmcapbonoxy radi xylene heated to 100 C. was addeddropwrse a solution cals. However, the oxygen atoms on silicon can also be Of 36 grams 1 of f symbls'gammaglycldoxy' attached to hydrogen, i.e. the hydroxyl radical on silicon Propyltetramethyldlslloxane 80 grams of The to give a silanol, or to another silicon atom to form a reaction mixture Was Stripped of eXCeSS diethylehe sfloxane 1i k amine and Volatiles at 190 C. and mm. Hg leaving Thus, the vorganosilicon compositions of this invention a moderately viscous fluid product of the formula To 80 grams of diethylene triamine in 40 grams of OH liegluez OH V HzNCH2CH:[NHCH2CHZNHCH2CHCH:O CHzCHzCHzSiO SiCHzCHzCHzO CH1CHCHzNHCHsCHzlaNHOHzCHzNI-I can be two silicon atoms joined by a linkage of this invention or chains of silicon atoms so joined or any combination of such groups joined together by a siloxane linkage.

A preferred species of this invention is an organopolysiloxane composition containing at least one unit of the formula This material was an excellent curing agent for both epoxide coating resins and epoxide casting resins.

Example 2 362 grams (1 mol) of (A) were added slowly to 412 grams (4 mols) of diethylene triamine heated to 180 C. When the almost instantaneous reaction was complete, the

Rm Rn reaction mixture was stripped of excess diethylene triamine at 190 C. and 1 mm. Hg. 530 grams of a light T amber fluid having a viscosity of 12,400 cs. at C. and

in which X and Y are as above defined, each Risa hydro- 11-6% y Weight Ilitfegell Wete PTOdUCed- This material gen atom, a hydroxyl radical, a monovalent hydrocarbon Was the Same as that EXahlple 1 and had Ihe formula radical, 1a monovalent hydrocarbonoxy radical, a monowhich has a theoretical nitrogen content of 111% y valent halogenohydrocarbon radical or a monovalent halo- Weight. genohydrocarbonoxy radical, all of which are defined above, each m has a value of from 0 to 3 and each n has a Value of from 0 to 2, any remaining units in said organopolysiloxane having the unit formula Example 3 181 grams (0.5 mol) of (A) were added slowly to 515 grams (5 mols) of diethylene triamine heated to 160 C. The temperature was maintained at 160 C. for 1 /2 hours after the addition was complete. The reaction mixture was then stripped of excess diethylene triamine at 180 C. and 1 mm. Hg. There resulted 275 grams of a clear 2 yellow fluid having a viscosity of 5,400 cs. at 25 C. and 39 a nitrogen content of 13.04% by weight. The formula of this compound is where R and m are as above defined.

OI-I MezMez OH HZNOH2CH2[NHCH2CH2NHOH2CHCHZO OHzCHzGHzSiOSiCHzCHzCHzO CHzCHCHZNHCHzCHzhNHCHzCHzNH: The polymers of this invention can be endblocked with Example 4 groups such as SiR (including The experiment of Example 3 was repeated including in the reaction system 0.5 gram of phenol. The time R of reaction was substantially decreased.

Si(XYR)z and si'XYR' 5 where X, Y, R and R are as above defined. If the epoxidized siloxane concentration in the epoxy-amine reaction system is greater than the amine concentration, the re- IefiuXhlg miXh-lfe Of 240 grams H1015) 0f sulting siloxanes will be epoxidized siloxy endblocked. ethylehediamihe and gram of Phenoh Afiel" reflux- It has been found that the presence of small amounts for One hour, the reaction miXhlfe pp of of phenol catalyzes the epoxide-amine reactions to proexcess ethylene diamihe and Volatiles at and duce the linkages of this invention at lower temperatures 405 grams of a fluid Product having a and in shorter periods of time than required for the pro- Viscosity of 20,000 at and hitrogeh Content duction of the same compositions without employing the Of 109% y Weight were produced- This Compound phenol catalyst. The amount of phenol necessary in the Was Example 5 362 grams (1 mol) of (A) were added slowly to a on MezMez OH H2N[C2H4NHCHZCHCHZO(CH2)3SiOsi(C Z)3 OH2OHCH2NH12C2H1NH2 system for catalysts is generally less than one percent by Example 6 weight. The term phenol is intended to include hy- 181 grams (05 mol) of (A) were added Slowly to droxylated aryl compounds generally and would include 170 Grams (1 mol) of menthanediamine such compounds as chlorophenol and bis-phenol. Mez Me All the compounds of this invention are useful as modifiers for any compatible resin system. They are especially 1 useful as curing agents for epoxide resins where there I NHZ remain in the agent some primary or secondary ami and 0.5 gram of phenol at 150 C. The reaction mixgwups Whlch Fa react lm epoxide ture was stirred and heated 1 hour at 190 C. and The composltlohs of thls z l whenhsed as curing stripped of excess menthanediamine and volatiles at 190 j are especlally efiefitlve m the curmg P P E C. and 2 mm. Hg with a nitrogen purge. There resulted Tesmsh P F hlgh temperature fiFXIblhty, 305 grams of a product found to contain 5.8% by weight proved acid resistance, increased compatabihty, decreased nitrogen and 109% by Weight Sill-COIL The thfioretical toxicity and decreased volatility in the final films as com- 7 amounts of nitrogen and Silicon in the 4:3 amine to P F to m Prepared 115mg only the correspondmg epoxide adduct are 5.78% by Weight nitrogen and 9.5% 31111116 as 1 agent by weight silicon. Most of the product consisted of The following examples are illustrative and are not misomers of the basic formula tended to limit this invention which is properly delineated in the claims.

0 H Me2Me2 O H HzNMNHCHzOHCHaO(OH2)aSiOSi (CHDaOCHa OHCHQNHJMNH:

where M is the radical M62 Me Example 7 36 grams (0.1 mol) of (A) were added slowly to 19 grams (0.11 mol) of menthanediamine and 0.5 gram of phenol in 30 grams of xylene heated to 150 C. The reaction mixture was refluxed for 3 hours. 15 grams of xylene were added to make a 55% by Weight solids solution having a viscosity of 210 cs. When this solution was used as a curing agent for an epoxy coating resin, the resultant coating had excellent thermal stability.

Example 8 170 grams (1 mol) of menthanediamine and 0.5 gram of phenol were refluxed in 200 grams of xylene. 362 grams 1 mol) of (A) were added slowly and refluxing was continued for one hour more. The result was a clear so- 8 Example OH M62 CHzCHOHnO(CHg)sSiO Example 1] 100 grams (0.5 mol) of methylenedianiline and 1 gram of phenol were refluxed in 100 grams of xylene.

Over a period of 5 hours 100 grams (0.27 mol) of (A) were added to the refluxing mixture. The mixture was refluxed one more hour and stripped of excess methylenedianiline and volatiles at 150 C. and 2 mm. Hg. There were obtained 190 grams of an amber tar of the formula OH MezMez OH HQN 2 NHCHZCHCHQO(CH2)3siOSi(CHz)aO CHzCHCHzNH 12CH NH? lution having a viscosity of 1000 cs. at C. Upon 25 prolonged heating this solution became a sticky rubber. Example 9 grams (0.75 mol) of rn-phenylenediamine and 0.5 gram of phenol were refluxed in 50 grams of xylene.

91 grams (0.25 mol) of (A) were added slowly. The 30 mixture was refluxed for 4 hours at to C. and

Epoxide coating resins cured with this agent gave light, hard films with greater flexibility and heat resistance than similar resins cured with methylenediamine.

Example 12 When 2 mols of mono-gamma-glycidoxypropylpentamethyldisiloxane are reacted with 1 mol of anhydrous ammonia in ethanol, the resulting product has the formula Meg OH on M69 ireasiosrouzonzomo omononmnomonomo OHzCHzCHzSiOSiMea subsequently stripped of excess m-phenylenediamine and volatiles at C. and 1 mm. Hg. There was obtained 135 grams of a tar which was Mixture of this composition with epoxy resins had good pot stability. Epoxide resins cured with this product were tougher and more heat stable than similar epoxide resins cured only with m-phenylenediamine.

Example 13 When 2 mols of the following organosilicon compounds are reacted with one mol of the following amines while refluxing in xylene solution, the adducts listed are produced:

Epoxide Amine Adduct O CHzCHg Phz P112 OH OH P112 CHzGHOHzOHzSlOI'I piperazine HOSiCHzCHaCHCHzN NCHzCHCH2CHzSiOH CHzCHz O OH OH OHQOHOI'IQCHZS1(OEU3 p-amino- (EtO)3S1CHzCHzCHCHzNCHzCHCHzCHgSi(OEt)3 benzoic acid.

0 ll COH O Q5H4C1 C HrCI OH I] OH CaHrCl CHzCHCHzCHzSKOEt); thioiem (ELO)2SiCHzCHzCHCHrNHNHCNHCHzOHCHaCHzSi(OEt)z car all 9 ll 0 CHzCFs C C HqCHZCFa I CH2 OH OH CHzCHCHqCHzS1 OCoH4CD 8113111611110 (OIC HiOhSiCHzCHwHOHZN NCHzCHCHzCHz- CHC CHzCHzCFa Si(OCoH4C1)2 OH H O I 3,046,250 1 1 12 under the conditions of Example 13, one of the products is (0E0: (out): MeSiCHzOHgCHzOGHQOHOOHzCHCH: 0H20H0omfililomocmomomsme NH C Example 17 Example 20 When 4 mols of guanidine are reacted with 3 mols of When 2 mols of under the conditions of Example 13, the product is s 0 si%11,0H,c H oHMe NE NH H OH MezPh Mez OH II NHz CNHCHQCHCHQOOH2CHZCHZS10%OS1OH2CHZCIIZOCIIfiOHCHiNH CNHz 0 AdezSlCHzCHzCHzOCHzCHCHg Example 18 are added slowly to 1 mol of ethylene diamine under When 1 mol of benzidine sulfone is reacted with 2 reflux condltlons the Product18 amlxture of mols of Me OH OH Me (MeSSiOMSiCHZCHZCHSIHNHOHzOHzNI-IlgH OHCHzCHzSi (O SiMes): B B

o C/H\CHOI-I OCH CH ori SM 0 0 Me 0H Me 2 2 2 2 2 l 2 u M (Me3SiO)gSiOHgOHQGHIOAHNHCHQOH NHCFHCHQCHQSKOSiMeQM 6 under the conditions of Example 13, the product is MeCHOH M62 Me: OH CH2CHCH2O CHzCHzCHzSiO (SiMeaO) 12SiCH2CH2CH2O CHzCHCHzNH Example 19 and When polysiloxanes containing the following units are I u e M reacted with {efluxmg ethylene dlamme a i 2 (MmSiO)QSiCHhOHZCHNHCH CHQNHCHCHQCHzSKOSiMeaM mols of the s1loXane unit per mol of ethylene diamlne,

the resulting products will include the units shown below. MQOHOH MeGHOH Epoxide Adduct 0 Me Me OH OH Me OS[i CHCH2 --O Si CHCHzNHCHzCHzNHCHzCH gl MeO Me Me Me Me Me Me OSliCH2CHCHzCH2C-CH2 -O SliCHzCHCH2CHzgHCHzNHCH2CH3NHCH ?)%Hr-CH2 ('IJHMe Me -OS[iCHi 0 Ph P11 OH OH O SliCH2CHzOH2OCH2CHCHz -OSliCH2CH2CH2OCHzCHCHzNHCEhCHzNHCHzCH CH1 Ph -)iCH1CH2CH2-O Met 0 C OH Me Me I Me OS|iCH2CH2CHCMe2 OiiCHzCHzCHNHCHzCHzNHCHCH2CH2%- C OH I Me:

O OH OH OH 01.5SlCHzCH2CHzO CHzCHCHgO CH2CHCH2 O1. SiCH2CH2CHaO CHzCHCHzO CH2CHCHZNCII 2 OH OH CH2 OmSiCHzCHzCHzOCH2CHCH2O CHzCHCHzNH 1 3 That which is claimed is: 1. An organopolysiloxane composition containing at least one unit of the formula Rm RD in which each Y is a divalent radical composed of atoms selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, metal and non-hydrolyzable halogen atoms and is attached to both X radicals by carbon-nitrogen bonds, said Y radical being free of acid groups having a dissociation constant greater than 10*, each X is a divalent organic radical connected to silicon by a silicon-carbon linkage and consisting of hydrogen atoms, carbon atoms and oxygen atoms, the latter being present in configurations of the group consisting of hydroxyl groups, epoxy groups and ether linkages, said X radical containing at least one pair of adjacent carbon atoms, one carbon atom of said pair being attached to a hydroxyl group and the other carbon atom of said pair being attached to a nitrogen atom of the radical Y, each R is a monovalent radical selected from the group consisting of the hydrogen atom, the hydroxyl radical, hydrocarbon radicals, halogenohydrocarbon radicals, hydrocarbonoxy radicals and halogenohydrocarbonoxy radicals, each m has a value of from to 3 and each n has a value of from O to 2, any remaining units of said organopolysiloxane having the formula RmSiO in which R and m are as above defined.

2. A composition of the formula in which each Y is a divalent radical composed of atoms selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, metal and non-hydrolyzable halogen atoms and is attached to two X radicals by carbon-nitrogen bonds, said Y radical being free of acid groups having a dissociation constant greater than each X is a divalent organic radical connected to silicon by a silicon-carbon linkage andconsisting of hydrogen atoms, carbon atoms and oxygen atoms, the latter being present in configurations of the group consisting of hydroxyl groups, epoxy groups and ether linkages, said X radical containing at least one pair of adjacent carbon atoms, one carbon atom of said pair being attached to a hydroxyl group and the other carbon atom of said pair being attached to a nitrogen atom of the radical Y, each R is a monovalent radical selected from the group consisting of the hydrogen atom, the hydroxyl radical, hydrocarbon radicals, halogenohydrocarbon radicals, hydrocarbonoxy radicals and halogenohydrocarbonoxy radicals, and a has an average value of from 2 to 4.

3. A composition of the formula OH R2 R2 OH HY[OH2CHCH2OCH1CHzOHzSiOSiOHzCHrCHzCOHzCHCHrYJH in which each Y is a divalent radical composed of atoms selected from the group consisting of carbon, hydrogen,

oxygen, nitrogen, sulfur, metal and non-hydrolyzable halogen atoms and is attached to carbon. by carbon-nitrogen bonds, said Y radical being free of acid groups having a dissociation constant greater than 10*, each R is a monovalent radical selected from the group consisting of the hydrogen atom, the hydroxyl radical, hydrocarbon radicals, halogenohydrocarbon radicals, hydrocarbonoxy radicals and halogenohydrocarbonoxy radicals, and a has an average value of from 2 to 4.

4. The composition of claim 3 in which each R is a methyl radical.

5. The composition of claim 3 in which each R is a phenyl radical.

6. The composition of claim 3 in which some R groups 35 are methyl radicals and the remainder of the R groups are phenyl radicals.

References Cited in the file of this patent UNITED STATES PATENTS 

1. AN ORGANIC ORGANOPOLYSILOXANE COMPOSITION CONTAINING AT LEAST ONE UNIT OF THE FORMULA 